200419315 玖、發明說明： (一） 發明所屬之技術術域 本發明係有關一種製造半導體裝置、平板顯示器（FPD) 等時使用的光阻圖案形成方法，特別是有關要求光阻膜具高 耐熱性的TFT(薄膜電晶體）主動矩陣步驟的方法之一、使用 半色調光罩之4光罩步驟（可減低光罩使用數的步驟）或適合 形成反射型TFT用波型形狀殘留材等之超高耐熱光阻圖案 形成方法。 (二） 先前技術 於以LSI等半導體積體電路、或Fpd之顯示面製造、熱 針頭等電路基板製造等爲首的廣泛範圍中，爲進行微細元件 形成或微細加工時，以往使用微影術技術。於微影術技術中 ’爲形成光阻圖案時使用正型或負型感光性組成物。此等感 光性組成物中正型感光性組成物可廣泛使用含有鹼可溶性 樹脂與作爲感光劑之醌二疊氮基二疊氮基化合物的組成物 。該組成物例如「酚醛清漆樹脂/醌二疊氮基化合物」有很 多文獻（例如專利文獻1〜4)記載各種組成。此等含有酚醛清 '漆樹脂與醌二疊氮基化合物之組成物，直至目前爲止就酚醛 清漆樹脂及感光劑而言進行硏究開發。 另外，於以往TFT主動矩陣基板之配列基板步驟中， 使用合計5張以上光罩。然而，高光罩化係爲製造成本高成 本化、步驟時間之長時間化或製造處理性降低的要因，爲解 決該問題進行檢討節省光罩化、即4光罩步驟。因此，提案 使用高開口率液晶顯示裝置少的光罩予以製造的方法（例如 -5- 200419315 參照專利文獻5)。 【專利文獻1】日本特公昭54-23570號公報（1頁） 【專利文獻2】日本特公昭56-30850號公報（1頁） 【專利文獻3】日本特公昭55-73045號公報（1〜4頁） 【專利文獻4】日本特公昭61-205933號公報（1頁、3〜5頁） 【專利文獻5】特開2002-9 8996號公報（2〜5頁） 上述節省光罩步驟，一般而言必須藉由半色調曝光形成 具有階差之光阻圖案進行乾式蝕刻步驟，爲提高該乾式蝕刻 時光阻膜之乾式蝕刻耐性時，對光阻圖案進行加熱處理。此 處，一般要求耐熱溫度爲130t以上，習知正型光阻在該加 熱步驟中會有圖案下垂等問題，必須藉由對應、改變較乾式 蝕刻條件更爲穩定的條件等方法以改善進行製造等之步驟 或提高正型光阻材料之耐熱性。 而且，爲反射型TFT時必須製作波型形狀等之殘材，且 於上濺射A1等高反射性金屬予以覆蓋，惟爲抑制水吸附或 金屬離子之移動時，或在反射型TFT板之步驟中該波型形狀 殘留物另添加 MIBK(甲基異丁酮）或THF(四氫呋喃）或 NMP(N-甲基-2-吡咯烷酮）等之有機溶劑。因此，對保持此等 溶劑而言之耐性時，必須後烘烤。然而，一般而言對習知正 型光阻劑進行1 3 0 °C以上之後烘烤時，會有流動、原有波型 形狀崩壞的問題。 (三）發明內容 ~ 6 - 200419315 發明所欲解決的問g頁 有鑑於上述情形，本發明係以提供於要求製造TFT主動 矩陣基板等、光阻圖案之局耐熱性步驟中，使用可形成良好 的超高耐熱正型圖案、正型感光性組成物之圖案形成方法爲 目的。 另外，本發明係以提供一種於要求製造TFT主動矩陣基 板等、光阻圖案之局耐熱性步驟中，使用半色調光罩形成具 有良好超高耐熱階差之圖案、或波型形狀之圖案、使用正型 感光性組成物之圖案形成方法爲目的。 鲁 解決問顆的手跺 本案發明人經過銳意的檢討，發現使用特定組成的正型 感光性組成物，於曝光、顯像後，進行全面曝光，視需要進 行熱處理，而可達成上述目的，終於完成本發明。 換言之，本發明係有關一種圖案形成方法，其特徵爲具 有[1]使含有（a)鹼可溶性樹脂、（b)具有醌二疊氮基之感光劑 、（c)光酸發生劑、（d)交聯劑及（e)溶劑之感光性組成物塗覆 於基板上的步驟，[2 ]通過光罩以進行曝光的步驟，[3 ]使該鲁 曝光部顯像去除以形成正型像的步驟，以及[4 ]進行全面曝光 的步驟。 另外，本發明係有關上述圖案形成方法中，於上述圖案 形成方法中，（b)具有醌二疊氮基之感光劑與（c)光酸發生劑 具有在相同曝光波長下之吸收活性，該全面曝光係在該感光 劑與光酸發生劑所共同具有吸收活性之曝光波長中進行。 此外，本發明係有關一種圖案形成方法，其特徵爲具有 200419315 [1]使含有（a)鹼可溶性樹脂、（f)具有醌二疊氮基、且作爲感 光劑及光酸發生劑功能的化合物（d)交聯劑及（e)溶劑之感光 性組成物塗覆於基材上的步驟，[2]通過光罩進行曝光之步驟 ’ [3]顯像去除該曝光部以形成正型像之步驟，以及[4]進行 全面曝光之步驟。 而且’本發明係有關於上述任何圖案形成方法中，於全 面曝光步驟後進行[5]加熱處理（後烘烤）。 另外’本發明係有關上述記載的任何圖案形成方法中， 於鹼可溶性樹脂爲至少一種選自於酚醛清漆樹脂、聚乙烯苯 β 酚系樹脂及丙烯酸系樹脂。 此外，本發明係有關上述記載的任何圖案形成方法中， 曝光步驟所使用的光罩係附有半透過膜或加入曝光裝置之 解像臨界以下尺寸之隙縫或篩網，部分存在光透過部之透過 率爲10〜90%半色調部之光罩。 於下述中更詳細說明本發明。 (四）實施方式 本發明感光性組成物中使用的酚醛清漆樹脂，可使用習 ® 知含有鹼可溶性樹脂與醌二疊氮基之感光劑的感光性組成 物中使用的酚醛清漆樹脂即可，沒有特別的限制。本發明中 較佳的酚醛清漆樹脂可藉由各種酚醛類單獨或數種混合物 以甲醛等醛類聚縮合製得。 構成該酚醛清漆樹脂之苯酚類例如苯酚、ρ-甲酚、m-甲 酚、〇-甲酚、2,3 -二甲基苯酚、2,4 -二甲基苯酚、2,5 -二甲基 苯酚、2,6 -二甲基苯酚、3,4-二甲基苯酚、3,5-二甲基苯酚、 -8- 200419315 2,3,4 -二甲基本酚、2,3,5 -二甲基苯酚、3,4,5-三甲基苯酚、 2，4,5-三甲基苯酚、伸甲基雙苯酚、伸甲基雙卜甲酚、間苯 一酚、兒余酚、2 -甲基間苯二酚、4 _甲基間苯二酚、〇 _氯苯 酚、m-氯苯酚、p-氯苯酚、2,3_二氯苯酚、甲氧基苯酚、 P-甲氧基苯酣、P-丁氧基苯酚、心乙基苯酚、乙基苯酚、 P -乙基苯g分、2，3 -二乙基苯酚、2,5 -二乙基苯酚、p-異丙基苯 酚、α-萘酚、β-萘酚等。此等可以單獨使用或數種混合物使 用。 而且，醛類例如甲醛、及對甲醛、乙醛、苯并醛、羥基 · 本并ii、氯乙醒等’此等可單獨使用或數種混合物使用。 本發明感光性組成物使用的酚醛清漆樹脂之重量平均 分子量以聚苯乙烯換算5,000〜100, 〇〇〇較佳、更佳者以聚苯 乙烯換算5,000〜50,000。 另外，鹼可溶性樹脂除酚醛清漆樹脂外，亦可以爲乙烯 苯酚系樹脂、或丙烯酸系樹脂。鹼可溶性丙烯酸系樹脂例如 丙烯酸酯及/或甲基丙烯酸酯與丙烯酸、甲基丙烯酸等不飽 和羧酸之共聚物。 ^ 另外，本發明感光性組成物使用的具有醌二疊氮基之感 光劑可以爲具有醌二疊氮基之感光劑即可，以藉由如萘醌二 疊氮基磺酸氯化物或二甲苯酮二疊氮基磺酸氯化物之醌二 疊氮基磺酸鹵化物、具有可與該酸鹵化物縮合反應的官能基 例如羥基、胺基等，尤以羥基更佳。具有羥基之低分子化合 物例如氫醌、間苯二酚、2,4-二羥基二苯甲酮、2,3,4-三羥基 二苯甲酮、2,4,6-三羥基二苯甲酮、2,4,4’-三羥基二苯甲酮 -9- 200419315 、2,3,4,4、四羥基二苯甲酮、2,2，，4,4、四羥基二苯甲酮、 2,2，3,4,6 -五經基一苯甲酮等，具有經基之高分子化合物例 如酹醛清漆樹脂、聚乙烯苯酚等。而且，醌二疊氮基磺酸鹵 化物與具有羥基之化合物的反應物可以爲單一酯化物、亦可 以爲酯化率不同的二種以上混合物。此等具有醌二疊氮基之 感光劑’一般而言於本發明中對1 〇〇重量份感光性組成物中 樹脂成分而言爲1〜30重量份。 本發明感光性組成物中使用的光酸發生劑（藉由放射線 照射產生酸之化合物）’只要是藉由放射線照射產生酸之化善 合物即可，沒有特別的限制。該化合物以例如習知化學放大 型光阻劑中作爲光酸發生劑較佳。該光酸發生劑有碘鑰鹽、 毓鹽、二偶氮鑰鹽、銨鹽、吡啶鹽等，含鹵素之化合物有含 鹵化烷基之烴化合物、含鹵化烷基之雜環式化合物等（鹵化 甲基三阱衍生物等），二偶氮酮化合物有1,3-二酮基-2-二偶 氮化合物、二偶氮二苯甲酮化合物、二偶氮萘醌化合物等， 楓化合物有β-酮颯、β-磺基楓等，磺酸化合物有烷基磺酸酯 、鹵化烷基磺酸酯、芳基磺酸酯、亞胺基磺酸酯等。此等可 β 以單獨使用或2種以上混合使用。 本發明感光性組成物使用的光酸發生劑以2-[2-(5-甲基 呋喃-2-基）乙烯基]-4,6-雙（三氯甲基）-s-三阱爲典型的三畊 系或 5-甲基磺醯氧基亞胺基- 5H-噻吩-2-茚基-2-甲基苯基乙 烯腈爲典型的氰系酸發生劑。光酸發生劑之配合量對1 00重 量份鹼可溶性樹脂而言通常爲0 · 0 5〜9重量份、較佳者爲0.5 〜3.0重量份更佳。 -10- 200419315 另外，含有醌二疊氮基之化合物使用1，2-萘醌二 -4 -磺醯基化合物時，該化合物可使用作爲感光劑，亦 作爲光酸發生劑，且上述（b)與（c)可以一種物質代用 本發明使用的交聯劑爲受到以放射線照射部發生 用’使鹼可溶性樹脂交聯、硬化者即可，沒有特別的 例如蜜胺系、苯并鳥糞胺系、尿素系交聯劑、多官能 氧基之化合物等各種交聯劑。蜜胺系、苯并鳥糞胺系 系等交聯劑中低分子交聯劑例如六羥甲基蜜胺、五羥 胺、四羥甲基蜜胺、六羥甲氧基甲基蜜胺、五甲氧基 胺及四甲氧基甲基蜜胺之羥甲基化蜜胺或其烷醚物、 基苯并鳥糞胺、四甲氧基甲基苯并鳥糞胺及三甲氧基 并鳥糞胺之羥甲基化苯并鳥糞胺或其烷醚體、N , N _二 尿素或其二烷基醚物、3,5 -雙（羥基甲基）過氫_ι，3,5--4 -酮（一經甲基糖酵酸內酯）或其院醚物、四經甲基乙 院基脲或其四甲醚物、2,6-雙（羥基甲基）_4-甲基苯酚 醚物、基-2,6-雙（羥基甲基）苯酚或其烷醚物、 -1，3 -雙（經基甲基）過氫_ι，3,5 -三畊_2_酮（N-乙基二經 D坐）或其院_物等較佳。而且，蜜胺系、苯并鳥糞胺 素系父聯劑中高分子交聯劑例如甲氧基甲基化蜜胺 、乙氧基甲基化蜜胺樹脂、丙氧基甲基化蜜胺樹脂、 甲基化蜜胺樹脂、甲氧基甲基化尿素樹脂、乙氧基甲 素樹S曰、丙氧基甲基化尿素樹脂、丁氧基甲基化尿素 較佳。此外，含有多官能性環氧基之化合物係在一分 有1個以上苯環或雜環、且含有2個以上環氧基之化 疊氮基 可使用 〇 的酸作 限制， 性含環 、尿素 甲基蜜 甲基蜜 四羥甲 甲基苯 羥甲基 噁二阱 二醛二 或其烷 5-乙基 甲基三 系、尿 系樹脂 丁氧基 基化尿 樹脂等 子中含 合物。 -11- 200419315 本發明使用的溶劑例如乙二醇單甲醚、乙二醇單甲醚等 之乙二醇單烷醚類、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙 酸酯等乙二醇單烷醚乙酸酯類、丙二醇單甲醚、丙二醇單乙 醚等丙二醇單烷醚類、丙二醇單甲醚乙酸酯、丙二醇單乙醚 乙酸酯等之丙二醇單烷醚乙酸酯等之丙二醇單烷醚乙酸酯 類、乳酸甲酯、乳酸乙酯等之乳酸酯類、甲苯、二甲苯等之 芳香族烴類、甲基乙酮、2-庚酮、環己酮等酮類、N，N-二甲 基乙醯胺、N-甲基吡咯烷酮（NMP)等醯胺類' γ-丁內酯等內 酯類。此等溶劑可以單獨使用或2種以上混合使用。 本發明使用的感光性組成物中視需要可配合黏合助劑及 界面活性劑等。黏合助劑例如烷基咪唑啉、丁酸、烷酸、聚 經基苯乙烯、聚乙烯基甲醚、t_丁基酚醛清漆樹脂、環氧基 砂烷、環氧基聚合物、矽烷等，界面活性劑例如非離子系界 面活性劑如聚醇類與其衍生物、即聚丙二醇、或聚環氧乙烷 月桂醚、含氟之界面活性劑例如弗羅賴頓（譯音）（商品名、住 友3M公司製）、梅卡法克（譯音）（商品名、大日本油墨化學 公司製）、史魯弗隆（譯音）（商品名、旭玻璃公司製）、或有機 矽氧烷界面活性劑例如KP34丨（商品名、信越化學公司製）。 而且’於特開平6 - 3 5 1 8 3號公報中記載製造濾色器之方法中 使用藉由酸硬化的樹脂、醌二疊氮基化合物、交聯劑、光酸 發生劑、染料、溶劑所成的濾色器形成用組成物。該方法以 製得解像度、耐熱性等優異的濾色器爲目的者，惟無法製得 如本發明製造半導體或TFT等要求之高解像性、超高耐熱性 者，且無法形成如本發明階差形狀、波型形狀等、視其目的 -12- 200419315 形成具有各種形狀、輪廓圖案者。其理由推測如下所述。換 言之’於上述濾色器形成用組成物中染料係爲使用作爲膜形 成成分之一，故被圖案曝光時使用的光或染料吸收，光無法 到達膜底部，結果解像度降低。上述濾色器用組成物對可得 濾、色器要求的數百微米之大圖案時沒有問題，惟無法形成使 用於要求數十微米〜數微米、或半微米之解像性的半導體或 TFT配列製造時所需的圖案。另外，於全面曝光時同樣地由 於光在膜途中被吸收，在膜下部不會產生必要的酸，無法引 起充分交聯，結果膜之耐熱性降低。此外，染料大多爲昇華 H 性高者’自膜中去除染料時步驟中裝置受到污染，且膜本身 爲多孔性，故會引起耐溶劑性或耐蝕刻性降低的缺點，爲沒 有昇華的染料時染料本身耐熱性低、膜之耐熱性亦低，故無 法製彳守。本發明中染料不爲任意成分者時，與上述濾色器用 組成物本質上不同’可形成半導體或TFT製造等要求的高解 像性、超高耐熱性光阻圖案者。 本發明之圖案形成方法係以步驟表示。首先，使上述感 光性組成物以旋轉塗覆、隙縫塗覆等方法塗覆於矽晶圓上或 H 玻璃基板等之基材上。基材係在表面上視需要設置有矽酸化 腠、鋁、鉬、鉻等金屬膜、I τ〇等之金屬氧化膜、以及半導 體兀件、電路圖案等。而且，塗覆法不受限於上述具體例示 者’以往塗覆感光性組成物時利用的塗覆法中任何方法皆可 。使感光性組成物塗覆於基材上後，使基板以對流式烤箱或 熱板等自7 0 C加熱至1 1 0 °c (預烘烤），去除溶劑成分，使上 述感光性組成物之薄膜形成於基材上。使該基材經由企求的 -1 3- 200419315 光罩予以圖案化時曝光。此時之曝光波長可以爲使習知感光 性組成物曝光利用的g線（4 3 6 n m)、h線（4 0 5 n m)、i線（3 6 5 n m) 、KrF(24 8nm)、ArF(193nm)等單波長、或g線與h線之混合 波長、g線與h線之混合波長、稱爲質子鍵結之使g線、h 線、i線混合者，任何者皆可。 於該圖案曝光後，藉由以鹼顯像液顯像，使曝光部溶出 ，且僅使未曝光部殘留，形成正型圖案。一般而言，鹼顯像 液有氫氧化四甲銨等之四級銨水溶液、或氫氧化鈉或氫氧化 鉀等無機氫氧化物水溶液。此處，使曝光部以顯像液溶出， 且使未曝光部殘留於基材上係爲成分（b)之具有醌二疊氮基 之感光劑藉由曝光使羧酸變化，且該羧酸具有鹼溶解性之故 。此時，即使同時在曝光部自成分（c)之酸發生劑產生酸，該 酸本身幾乎不會影響圖案曝光。 然後，使顯像完成的圖案基材再次以圖案曝光所使用的 相同曝光波長，不經由光罩或使用空白光罩（全部光透過）， 進行全面曝光。使全面曝光完成的基材藉由以對流式烤箱或 熱板等自1 1(TC加熱至160°C (後烘烤）使膜烘烤硬化。此處， 爲使藉由全面曝光、最初的圖案曝光時未曝光部曝光時，自 成分（c)之酸發生劑產生酸，該酸作爲觸媒，然後藉由後烘烤 使成分（a)之鹼可溶性樹脂與成分（d)之交聯劑引起交聯反應 ，可形成堅固膜。 該交聯由於具有後烘烤之熱且進行硬化，故可保持顯像 後之形狀且進行硬化◦而且，習知正型感光性組成物與習知 步驟於後烘烤中需以120 °C附近以上之溫度時’會引起圖案 200419315 崩壞、變成圓形的問題，惟本發明不會引起該現象。另外， 本發明使用較線•與•間隙或點或孔等一般圖案、部分具有 半色調部之光罩，包含使光阻以中途厚度殘留的凹凸形狀之 圖案，以及對形成波型形狀的圖案化而言可實現後烘烤後之 商耐熱性。 光罩中上述半色調部例如使非晶型矽膜、氮化矽膜、鉻 膜等爲適當厚度之半透過膜配置於光罩之所定部（設置），或 是曝光裝置之解像臨界以下尺寸之隙縫或篩網圖案藉由設 置所定部，可形成光透過部之透過率爲10 %〜90 %。而且，β 進行波型形狀圖案時，例如光罩以曝光裝置之解像臨界以下 使解像臨界附近之線•與·間隙圖案設置光罩。 於上述中係爲感光性組成物含有感光劑與光酸發生劑 者之例，如上所述本發明使用具有感光劑與光酸發生劑功能 之單一化合物時，以與上述相同的步驟形成耐熱性圖案。此 外’於上述中係表示對感光劑及光酸發生劑具有對相同曝光 波長之吸收活性的化合物例。該對感光劑及光酸發生劑具有 對相同曝光波長之吸收活性的化合物時，可使用圖案曝光與 β 全面曝光相同的曝光裝置實施，由於不需準備二種曝光裝置 、故較佳，本發明之圖案形成方法不受此所限制。此時，使 圖案曝光與全面曝光之曝光波長作爲感光劑及酸發生劑之 各感光波長以實施曝光。 【實施例】 於下述中藉由實施例更具體地說明本發明，惟本發明之 形態不受此等實施例所限制。 -15- 200419315 合成例1 (酚醛清漆樹脂之合成） 對100重量份甲酚/p-甲酚以6/4比例混合的混合甲 酚而言加入5 6重量份的3 7重量％甲醛、2重量份草酸，在 反應溫度1 00 °C下藉由常法反應5小時。該酚醛清漆樹脂之 分子量以聚苯乙烯換算爲15,2〇〇。 合成例2(感光劑之合成） 使2，3,4-三羥基二苯甲酮與丨，2-萘醌二疊氮基-5-磺醯基 氯化物以1/2.0加入比（莫耳比）溶解於二噁烷酸中，以三乙 胺作爲觸媒藉由常法予以酯化。使所成的酯藉由HPLC(高速 液體色層分析法）測定時，二酯2 9 %、三酯6 3 %。 合成例3 (感光劑兼酸發生劑之合成） 使2,3,4-三羥基二苯甲酮與萘醌二疊氮基-4-磺醯基 氯化物以1/2.0加入比（莫耳比）溶解於二噁烷酸中，以三乙 胺作爲觸媒藉由常法予以酯化。使所成的酯藉由HPLC (高速 液體色層分析法）測定時，二酯2 5 %、三酯6 1 %。 實施例1 對1 00重量份合成例1之酚醛清漆樹脂而言使1 7重量 份合成例2之感光劑、1重量份酸發生劑之2-[2-(5-甲基呋喃 -2-基）乙烯基]-4,6-雙（三氯甲基）-S-三阱、與5重量份作爲交 聯劑之甲氧基甲基化蜜胺樹脂的賽梅魯（譯音）3 00(三井賽迪 克（譯音）製）溶解於丙二醇單甲醚乙酸酯，爲防止於旋轉塗覆 時可在光阻膜上形成放射線皺摺、即爲防止條紋時添加 5 00ppm氟系界面活性劑、弗羅來頓（譯音）F-47 2 (住友史里耶 姆（譯音）公司製），另攪拌後，以〇·2μπι過濾器過濾，調製本 200419315 發明之感光性組成物。使該組成物旋轉塗覆於4吋砂晶圓上 ，在1 0 0 °C下、在熱板上預烘烤9 0秒後，製得3 μ m厚度光 阻膜。在該光阻膜上以具有g + h線混合波長之理光（譯音） 製分檔曝光器FX-604F ’經由光罩進行圖案曝光後，以2.38% 氫氧化四甲銨水溶液攪拌顯像6 0秒。圖案曝光係顯像厚之 光阻圖案與光罩設計，以5 μηι線•與·間隙爲1 : 1解像的 曝光能量作爲適當感度予以曝光。顯像後，以SEM(掃描電 子顯微鏡）觀察5 μηι線•與•間隙之截面觀察。結果如表丄（ 顯像後）表示。如表1可知，正常形成矩形圖案。 · 直至該顯像完成的基板以與圖案曝光使用者相同的曝 光裝置’使用空白光罩（全部透過光）進行全面曝光，然後， 使基板在1 2 0 °C、1 4 0 °C、1 6 0 °C之各熱板上，藉由秒加熱進 行後烘烤。以各種溫度進行後烘烤後之圖案截面以SEM觀 察。結果如表1所示。表1所示可知在14(TC下烘烤，維持 顯像後之矩形，在1 60 °C下僅在上部帶有大約圓形可維持高 耐熱性。 比較例1 · 於實施例1使用的組成物中，使用去除酸發生劑之 2-[2-(5-甲基呋喃-2-基）乙烯基μ4,6-雙（三氯甲基）-s-三哄之 組成物作爲感光性組成物外，與實施例1相同地進行圖案形 成及圖案形狀。結果如表1所示。如表1所示，顯像後形成 沒有問題之矩形圖案者，在1 20°C下後烘烤時在上部爲圓形 在140C下圖条底部開始流動變寬，在160C下完全流動 線間互連，無法得到充分的耐熱性。 -17- 200419315 比較例2 除於實施例1之圖案形成中無法全面曝光外，與實施例 1相同地進行圖案形成及圖案形狀觀察。結果如表1所示。 如表1所示，與比較例1完全相同，顯像後形成沒有問題的 矩形圖案，在120°C下後烘烤在上部爲圓形，在140°C下圖 案底部流動、開始變寬，在1 60 °c下完全流動線間相連，無 法得到充分的耐熱性。 實施例2 除使實施例1之感光性組成物之感光劑及酸發生劑改 β 成藉由合成例3之兼具感光劑及光酸發生劑的合成物外，與 實施例1相同地進行圖案形成及圖案形狀之觀察。結果如表 1所示。如表1所示，與實施例1之結果相同地在12 01：、 I40°c下烘烤時顯像後可維持顯像後之矩形，在16(rc下僅上 部帶有圓形，維持高的耐熱性。200419315 (1) Description of the invention: (1) The technical field to which the invention belongs The present invention relates to a method for forming a photoresist pattern used in the manufacture of semiconductor devices, flat panel displays (FPD), etc., and particularly relates to the requirement of a photoresist film with high heat resistance One of the methods of TFT (thin film transistor) active matrix step, four mask steps using halftone masks (steps that can reduce the number of masks used), or ultra-thin materials suitable for forming wave-shaped residual materials for reflective TFTs, etc. High heat-resistant photoresist pattern forming method. (2) The conventional technology has been used in a wide range of fields such as semiconductor integrated circuits such as LSIs, display surface manufacturing of Fpd, and circuit board manufacturing such as hot needles, etc. In the past, lithography was used for the formation of fine elements or microfabrication technology. In the lithography technique, a positive or negative photosensitive composition is used when forming a photoresist pattern. Among these photosensitive compositions, compositions containing an alkali-soluble resin and a quinonediazidediazide compound as a photosensitizer can be widely used as the positive type photosensitive composition. There are many documents (e.g., Patent Documents 1 to 4) describing various compositions of this composition such as "Novolac resin / quinonediazide-based compound". These compositions containing novolac lacquer resin and quinonediazide-based compounds have been researched and developed for novolac resins and sensitizers until now. In addition, in the step of arranging substrates of a conventional TFT active matrix substrate, a total of five or more photomasks were used. However, the photomask formation is a factor of high manufacturing cost, prolonged step time, or reduction in manufacturing processability. In order to solve this problem, it is reviewed to save photomask formation, that is, four photomask steps. Therefore, a method is proposed in which a mask with a small number of liquid crystal display devices with a high aperture ratio is manufactured (for example, -5- 200419315, refer to Patent Document 5). [Patent Document 1] Japanese Patent Publication No. 54-23570 (1 page) [Patent Literature 2] Japanese Patent Publication No. 56-30850 (1 page) [Patent Literature 3] Japanese Patent Publication No. 55-73045 (1 ~ 4 pages) [Patent Literature 4] Japanese Patent Publication No. 61-205933 (1 page, 3 to 5 pages) [Patent Literature 5] Japanese Patent Publication No. 2002-9 8996 (2 to 5 pages) Generally speaking, a dry etching step must be performed by forming a photoresist pattern having a step difference by halftone exposure. In order to improve the dry etching resistance of the photoresist film during the dry etching, the photoresist pattern is heat-treated. Here, it is generally required that the heat-resistant temperature is 130t or more. It is known that positive photoresists have problems such as pattern sagging during this heating step. It is necessary to improve the manufacturing by corresponding methods, such as changing conditions that are more stable than dry etching conditions. This step may improve the heat resistance of the positive photoresist material. In addition, when it is a reflective TFT, it is necessary to make a residual material such as a wave shape and cover it by sputtering a highly reflective metal such as A1. However, in order to suppress water adsorption or the movement of metal ions, or in a reflective TFT panel, An organic solvent such as MIBK (methyl isobutyl ketone), THF (tetrahydrofuran), or NMP (N-methyl-2-pyrrolidone) is added to the wave-shaped residue in the step. Therefore, post-baking is necessary to maintain the resistance of these solvents. However, in general, when a conventional positive photoresist is baked at a temperature of more than 130 ° C, it may cause problems such as flow and collapse of the original wave shape. (III) Content of the Invention ~ 6-200419315 The problem to be solved by the invention In view of the above situation, the present invention is provided in the step of local heat resistance of photoresist patterns, which requires the manufacture of TFT active matrix substrates, etc., which can form a good The purpose is to form an ultra-high heat-resistant positive pattern and a pattern forming method of a positive photosensitive composition. In addition, the present invention is to provide a pattern having a good ultra-high heat resistance step or a wave-shaped pattern using a half-tone mask in a step of local heat resistance of a photoresist pattern required to manufacture a TFT active matrix substrate or the like. The purpose is to form a pattern using a positive photosensitive composition. Lu Jiwen's hand 颗 After an intensive review, the inventor of the case found that using a positive-type photosensitive composition with a specific composition, after exposure and development, comprehensive exposure was performed, and heat treatment was performed as needed to achieve the above purpose, and finally The present invention has been completed. In other words, the present invention relates to a pattern forming method, which is characterized by having [1] a photosensitizer containing (a) an alkali-soluble resin, (b) a photosensitizer having a quinonediazide group, (c) a photoacid generator, and (d) ) A step of applying a photosensitive composition of a crosslinking agent and (e) a solvent to a substrate, [2] a step of exposing through a photomask, and [3] developing and removing the exposed portion to form a positive image. Steps, and [4] steps for full exposure. In addition, the present invention relates to the above pattern forming method. In the above pattern forming method, (b) the photosensitizer having a quinonediazide group and (c) the photoacid generator have absorption activities at the same exposure wavelength. The full exposure is performed at an exposure wavelength in which the photosensitizer and the photoacid generator have absorption activity in common. In addition, the present invention relates to a pattern forming method, which is characterized by having a compound containing 200419315 [1] which contains (a) an alkali-soluble resin, (f) has a quinonediazide group, and functions as a photosensitizer and a photoacid generator. (D) a step of applying a photosensitive composition of a cross-linking agent and (e) a solvent to a substrate, [2] a step of exposing through a photomask '[3] developing and removing the exposed portion to form a positive image Steps, and [4] steps for full exposure. Furthermore, the present invention relates to any of the above-mentioned pattern forming methods, in which the [5] heat treatment (post-baking) is performed after the full exposure step. In addition, the present invention relates to any of the pattern forming methods described above, wherein the alkali-soluble resin is at least one kind selected from a novolac resin, a polyvinyl benzene β-phenol resin, and an acrylic resin. In addition, in the present invention, in any of the pattern forming methods described above, the photomask used in the exposure step is provided with a semi-transmissive film or a gap or screen with a size below the resolution threshold of the exposure device, and some of the light transmitting portions exist. A mask with a transmittance of 10 to 90% at the halftone portion. The present invention is described in more detail below. (4) Embodiment The novolak resin used in the photosensitive composition of the present invention may be a novolak resin used in a photosensitive composition containing an alkali-soluble resin and a quinonediazide-based photosensitive agent. There are no special restrictions. The preferred novolak resin in the present invention can be prepared by polycondensation of various phenols alone or in a mixture of several aldehydes such as formaldehyde. Examples of the phenols constituting the novolac resin include phenol, p-cresol, m-cresol, 0-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. Phenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, -8-200419315 2,3,4-dimethylphenol, 2,3,5 -Dimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylidene bisphenol, methylidene biscresol, resorcinol, catechol , 2-methylresorcinol, 4-methylresorcinol, 0-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, methoxyphenol, P-methyl Oxyphenylhydrazone, P-butoxyphenol, cardioethylphenol, ethylphenol, P-ethylbenzene g, 2,3-diethylphenol, 2,5-diethylphenol, p-iso Propylphenol, α-naphthol, β-naphthol and the like. These can be used singly or in combination. Further, aldehydes such as formaldehyde, and para-formaldehyde, acetaldehyde, benzoaldehyde, hydroxybenzyl, chloroethene, etc. can be used singly or in combination. The weight average molecular weight of the novolak resin used in the photosensitive composition of the present invention is 5,000 to 100,000 in terms of polystyrene, more preferably 5,000 to 50,000 in terms of polystyrene. The alkali-soluble resin may be a vinyl phenol resin or an acrylic resin in addition to the novolak resin. The alkali-soluble acrylic resin is, for example, a copolymer of an acrylate and / or a methacrylate and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid. ^ In addition, the photosensitizer having a quinonediazide group used in the photosensitive composition of the present invention may be a photosensitizer having a quinonediazide group, such as a naphthoquinonediazidesulfonic acid chloride or The quinonediazidesulfonic acid halide of toluonediazidesulfonic acid chloride has a functional group such as a hydroxyl group, an amino group, etc., which is capable of condensing with the acid halide, and a hydroxyl group is particularly preferred. Low molecular compounds with hydroxyl groups such as hydroquinone, resorcinol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone Ketone, 2,4,4'-trihydroxybenzophenone-9-200419315, 2,3,4,4, tetrahydroxybenzophenone, 2,2,4,4, tetrahydroxybenzophenone , 2,2,3,4,6-pentamentyl-benzophenone and the like, polymer compounds having a warp group such as acetal varnish resin, polyvinyl phenol and the like. The reaction product of the quinonediazidesulfonic acid halide and the compound having a hydroxyl group may be a single esterified product or a mixture of two or more different esterified rates. These photosensitizers having a quinonediazide group are generally 1 to 30 parts by weight for 100 parts by weight of the resin component in the photosensitive composition in the present invention. The photoacid generator (a compound that generates an acid upon irradiation with radiation) used in the photosensitive composition of the present invention is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation. This compound is preferably used as a photoacid generator among conventional chemically amplified photoresists, for example. The photoacid generator includes iodine key salt, sulphate salt, diazo key salt, ammonium salt, pyridine salt, etc. The halogen-containing compounds include halogenated alkyl-containing hydrocarbon compounds, halogenated alkyl-containing heterocyclic compounds, etc. ( Halogenated methyl triple well derivatives, etc.), diazones are 1,3-diketo-2-diazo compounds, diazobenzophenone compounds, diazonaphthoquinone compounds, etc., maple compounds There are β-ketone hydrazone, β-sulfo maple and the like, and sulfonic acid compounds include alkyl sulfonate, halogenated alkyl sulfonate, aryl sulfonate, and imino sulfonate. These can be used singly or in combination of two or more. The photoacid generator used in the photosensitive composition of the present invention uses 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-triple as A typical cultivar or 5-methylsulfonyloxyimino-5H-thiophen-2-inyl-2-methylphenylvinylnitrile is a typical cyanic acid generator. The compounding amount of the photoacid generator is usually from 0.005 to 9 parts by weight, and more preferably from 0.5 to 3.0 parts by weight, based on 100 parts by weight of the alkali-soluble resin. -10- 200419315 In addition, when a compound containing a quinonediazide group is a 1,2-naphthoquinone di-4 -sulfofluorenyl compound, the compound can be used as a photosensitizer and a photoacid generator, and (b ) And (c) can be used as a substitute for the cross-linking agent used in the present invention, and it is only necessary to cross-link and harden the alkali-soluble resin for generation of a radiation-irradiated part, and there are no special examples such as melamine and benzoguanamine System, urea system crosslinking agent, polyfunctional oxy compounds and other crosslinking agents. Low-molecular crosslinking agents such as melamine-based, benzoguanamine-based crosslinking agents such as hexamethylolmelamine, pentahydroxyamine, tetramethylolmelamine, hexamethylolmethylmelamine, pentamethylol Methylolated melamine or its alkyl ethers of methoxyamine and tetramethoxymethylmelamine, benzobenzoguanamine, tetramethoxymethylbenzoguanamine and trimethoxybenzoguanamine Hydroxymethylated benzoguanamine or alkane ethers of fecal amines, N, N _ diurea or its dialkyl ethers, 3,5-bis (hydroxymethyl) perhydro_ι, 3,5 --4-ketone (monomethylglycolactone) or its ether, tetramethyl methyl ethylurea or its tetramethyl ether, 2,6-bis (hydroxymethyl) _4-methyl Phenol ethers, radicals-2,6-bis (hydroxymethyl) phenol or their alkyl ethers, -1,3-bis (transmethyl) perhydro_ι, 3,5 -three-cultivation_2_one (N-ethyl two via D seat) or its hospitals, etc. are preferred. In addition, polymer crosslinking agents such as methoxymethylated melamine, ethoxymethylated melamine resin, and propoxymethylated melamine resin in the melamine-based and benzoguanamine-based parental crosslinking agents , Methylated melamine resin, methoxymethylated urea resin, ethoxymethylated tree S, propoxymethylated urea resin, butoxymethylated urea are preferred. In addition, compounds containing polyfunctional epoxy groups have one or more benzene rings or heterocyclic rings and one or more azido groups containing two or more epoxy groups. The acid can be used as a limit. Urea methyl melyl methyl tetromethylol benzyl methylol oxadialdehyde dialdehyde or its alkane 5-ethylmethyl tertiary, urinary resin butoxylated urinary resin, etc. . -11- 200419315 The solvents used in the present invention such as ethylene glycol monomethyl ether, ethylene glycol monoalkyl ethers of ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Ethyl glycol monoalkyl ether acetates, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and other propylene glycol monoalkyl ether acetates Propylene glycol monoalkyl ether acetates, lactates such as methyl lactate, ethyl lactate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone , N, N-dimethylacetamide, N-methylpyrrolidone (NMP) and other amines such as γ-butyrolactone and other lactones. These solvents can be used alone or in combination of two or more. The photosensitive composition used in the present invention may be compounded with an adhesion aid, a surfactant, and the like, as necessary. Adhesives such as alkylimidazoline, butyric acid, alkanoic acid, polystyrene, polyvinyl methyl ether, t-butyl novolac resin, epoxy sarane, epoxy polymer, silane, etc. Surfactants such as non-ionic surfactants such as polyalcohols and their derivatives, namely polypropylene glycol or polyethylene lauryl ether, and fluorine-containing surfactants such as Floriston (trade name, Sumitomo 3M company), Mekafak (transliteration) (trade name, Dainippon Ink Chemical Co., Ltd.), Schlufron (transliteration) (trade name, manufactured by Asahi Glass Co., Ltd.), or an organosiloxane surfactant such as KP34 丨 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Further, 'Yukkai Hei 6-3 5 1 8 3 describes that a method for manufacturing a color filter uses a resin hardened by an acid, a quinonediazide compound, a crosslinking agent, a photoacid generator, a dye, and a solvent. The resulting composition for forming a color filter. This method aims at producing color filters with excellent resolution and heat resistance. However, it is not possible to obtain those with high resolution and ultra high heat resistance required by the present invention for manufacturing semiconductors or TFTs. Step shapes, wave shapes, etc., depending on the purpose -12-200419315 Form those with various shapes and contour patterns. The reason is presumed as follows. In other words, the dye used in the above-mentioned color filter forming composition is used as one of the film forming components, so it is absorbed by the light or dye used in the pattern exposure, and the light cannot reach the bottom of the film, resulting in a decrease in resolution. The above-mentioned composition for color filters has no problem in obtaining large patterns of hundreds of microns required by filters and color filters, but it cannot form a semiconductor or TFT array that requires resolution of tens of microns to several microns or half microns. The pattern required during manufacture. In addition, during full exposure, similarly, since light is absorbed in the middle of the film, a necessary acid is not generated in the lower portion of the film, and sufficient crosslinking cannot be caused. As a result, the heat resistance of the film is reduced. In addition, most of the dyes are those with high sublimation H. The device is contaminated during the step of removing the dye from the film, and the film itself is porous, so it will cause the disadvantage of reduced solvent resistance or etching resistance. When there is no sublimation dye, The dye itself has low heat resistance, and the heat resistance of the film is also low. When the dye is not an arbitrary component in the present invention, it is substantially different from the composition for a color filter described above, and it can form a photoresist pattern with high resolution and ultra-high heat resistance required for semiconductor or TFT production. The pattern forming method of the present invention is represented by steps. First, the photosensitive composition is applied to a silicon wafer or a substrate such as an H glass substrate by spin coating, slit coating, or the like. The substrate is provided on the surface with a metal film such as silicic acid, aluminum, molybdenum, chromium, a metal oxide film such as I τ0, a semiconductor element, a circuit pattern, and the like, as required. Furthermore, the coating method is not limited to the specific exemplified above, and any of the coating methods used in the past for coating a photosensitive composition may be used. After the photosensitive composition is coated on the substrate, the substrate is heated from 70 ° C. to 110 ° C. (pre-baking) in a convection oven or a hot plate, and the solvent component is removed to make the photosensitive composition. The thin film is formed on a substrate. The substrate was exposed when patterned through a desired -1 3- 200419315 mask. The exposure wavelength at this time may be g-line (4 3 6 nm), h-line (40 5 nm), i-line (3 6 5 nm), KrF (24 8 nm), Any single wavelength such as ArF (193nm), or a mixed wavelength of g-line and h-line, a mixed wavelength of g-line and h-line, and a mixed g-line, h-line, and i-line called a proton bond may be used. After the pattern is exposed, the exposed portion is eluted by developing with an alkali developing solution, and only the unexposed portion is left to form a positive pattern. Generally, the alkali developing solution is a quaternary ammonium aqueous solution such as tetramethylammonium hydroxide or an inorganic hydroxide aqueous solution such as sodium hydroxide or potassium hydroxide. Here, the exposed part is dissolved in a developing solution, and the unexposed part is left on the substrate as the component (b). The photosensitizer having a quinonediazide group changes the carboxylic acid by exposure, and the carboxylic acid is changed. It has alkali solubility. At this time, even if an acid is generated from the acid generator of the component (c) in the exposure portion at the same time, the acid itself hardly affects the pattern exposure. Then, the developed patterned substrate is exposed again at the same exposure wavelength used for the pattern exposure, and a full exposure is performed without going through a mask or using a blank mask (all light is transmitted). The substrate exposed to full exposure is cured by convection oven or hot plate from 1 1 (TC to 160 ° C (post-bake)) to harden the film. Here, the first When the unexposed part is exposed during pattern exposure, an acid is generated from the acid generator of the component (c), and the acid serves as a catalyst, and then the alkali-soluble resin of the component (a) and the component (d) are crosslinked by post-baking. The agent causes a cross-linking reaction to form a strong film. This cross-linking has the heat of post-baking and hardens, so it can maintain the shape after development and harden. Also, it is known that the positive photosensitive composition and the conventional steps In post-baking, when the temperature is around 120 ° C or higher, the pattern 200419315 will cause the problem of the pattern 200419315 to collapse and become round, but the present invention will not cause this phenomenon. In addition, the present invention uses a line • and • gap or General patterns, such as dots or holes, and masks with halftone parts, include patterns with uneven shapes that leave the photoresist at a mid-thickness, and heat resistance after post-baking for patterning to form a wave shape The above-mentioned halftone part in the mask For example, a semi-transmissive film with an appropriate thickness such as an amorphous silicon film, a silicon nitride film, or a chromium film is arranged at a predetermined portion (setting) of a photomask, or a slit or a screen pattern with a size below the resolution of an exposure device By setting the predetermined portion, the transmittance of the light transmitting portion can be formed from 10% to 90%. In addition, when β is wave-shaped pattern, for example, the photomask is a line near the resolution threshold of the exposure device, which is near the resolution threshold. A photomask is provided with a gap pattern. The above-mentioned examples are those in which the photosensitive composition contains a photosensitizer and a photoacid generator. As described above, when a single compound having the functions of a photosensitizer and a photoacid generator is used in the present invention, The same steps as above are used to form a heat-resistant pattern. In addition, in the above, examples of compounds having absorption activity to the same exposure wavelength to the photosensitizer and photoacid generator are shown. The pair of photosensitizer and photoacid generator has the same exposure For wavelength-absorbing compounds, it can be implemented by using the same exposure device as pattern exposure and β full exposure. Since there is no need to prepare two types of exposure devices, it is better. The formation method is not limited to this. At this time, the exposure wavelengths of the pattern exposure and the full exposure are used as the respective photosensitive wavelengths of the photosensitizer and the acid generator to perform the exposure. [EXAMPLES] In the following, examples will be used to be more specific. The present invention is explained, but the form of the present invention is not limited by these examples. -15- 200419315 Synthesis Example 1 (Synthesis of Novolac Resin) 100 parts by weight of cresol / p-cresol mixed in a ratio of 6/4 For mixed cresol, 56 parts by weight of 37% by weight formaldehyde and 2 parts by weight of oxalic acid are added, and the reaction is carried out at a reaction temperature of 100 ° C for 5 hours by a conventional method. The molecular weight of the novolak resin is calculated as polystyrene. 15,200. Synthesis Example 2 (Synthesis of Photosensitizer) 2,3,4-trihydroxybenzophenone and 丨, 2-naphthoquinonediazide-5-sulfonyl chloride were mixed with 1 / The addition ratio (mole ratio) of 2.0 was dissolved in dioxane acid, and triethylamine was used as a catalyst for esterification by a conventional method. When the resulting ester was measured by HPLC (high-speed liquid chromatography), the diester was 29% and the triester 63%. Synthesis Example 3 (Synthesis of Photosensitizer and Acid Generator) 2,3,4-trihydroxybenzophenone and naphthoquinonediazide-4-sulfonyl chloride were added at a ratio of 1/2. Ratio) is dissolved in dioxane acid, and triethylamine is used as a catalyst for esterification by a conventional method. When the resulting ester was measured by HPLC (high-speed liquid chromatography), the diester was 25% and the triester was 61%. Example 1 For 100 parts by weight of the novolak resin of Synthesis Example 1, 17 parts by weight of the photosensitizer of Synthesis Example 2 and 1 part by weight of the acid generator 2- [2- (5-methylfuran-2- (Vinyl) vinyl] -4,6-bis (trichloromethyl) -S-triple, Semeru with 5 parts by weight of a methoxymethylated melamine resin as a crosslinking agent (transliteration) 3 00 (Manufactured by Mitsui Seidick) dissolved in propylene glycol monomethyl ether acetate, in order to prevent the formation of radiation wrinkles on the photoresist film during spin coating, that is, to add 5,000 ppm of fluorine-based surfactant when preventing streaks F-47 2 (manufactured by Sumitomo Siriem Co., Ltd.). After stirring, it is filtered through a 0.2 μm filter to prepare the photosensitive composition of the invention of 200419315. The composition was spin-coated on a 4-inch sand wafer, and pre-baked on a hot plate at 100 ° C for 90 seconds to obtain a 3 μm-thick photoresist film. On the photoresist film, a pattern exposurer FX-604F made by Ricoh (transliteration) with a mixed wavelength of g + h line was used for pattern exposure through a photomask, followed by stirring and development with a 2.38% tetramethylammonium hydroxide aqueous solution. 6 0 second. The pattern exposure is based on the development of a thick photoresist pattern and a mask design. The exposure energy with a 5 μm line and AND gap of 1: 1 is exposed as an appropriate sensitivity. After imaging, observe the cross section of the 5 μηι line and the gap with a SEM (scanning electron microscope). The results are shown in Table 丄 (after development). As can be seen from Table 1, a rectangular pattern was formed normally. · Until the developed substrate is exposed in the same exposure device as the pattern exposure user ', use a blank mask (all transmitted light) for full exposure, and then place the substrate at 120 ° C, 140 ° C, 1 Post-baking was performed on each hot plate at 60 ° C by heating in seconds. The cross section of the pattern after post-baking at various temperatures was observed by SEM. The results are shown in Table 1. As shown in Table 1, it can be seen that baking is performed at 14 ° C, and the developed rectangle is maintained. At 160 ° C, only the upper part is rounded to maintain high heat resistance. Comparative Example 1 · Used in Example 1 In the composition, a composition in which 2- [2- (5-methylfuran-2-yl) vinyl μ4,6-bis (trichloromethyl) -s-trioxine is removed from the acid generator is used as a photosensitizer. Except for the composition, pattern formation and pattern shape were performed in the same manner as in Example 1. The results are shown in Table 1. As shown in Table 1, those who formed rectangular patterns without problems after development were post-baked at 120 ° C. At the top, it is circular. At the bottom of the bar at 140C, the flow starts to widen. At 160C, the interconnection between the lines completely flows, and sufficient heat resistance cannot be obtained. -17- 200419315 Comparative Example 2 Except in the pattern formation of Example 1 Except that full exposure was not possible, pattern formation and pattern shape observation were performed in the same manner as in Example 1. The results are shown in Table 1. As shown in Table 1, it was exactly the same as Comparative Example 1. A rectangular pattern was formed without any problem after development. After baking at 120 ° C, the upper part is circular, at 140 ° C, the bottom of the pattern flows and starts to widen, at 1 60 ° c The complete flow lines are connected, and sufficient heat resistance cannot be obtained. Example 2 Except that the photosensitizer and the acid generator of the photosensitive composition of Example 1 were changed to β by the combination of the photosensitizer and the photoacid generator in Synthesis Example 3 Except for the composition of the agent, pattern formation and pattern shape were observed in the same manner as in Example 1. The results are shown in Table 1. As shown in Table 1, the results were the same as in Example 1 at 12 01 :, I40 ° c. After baking, the rectangle after development can be maintained after development, and only the upper part is rounded under 16 (rc), maintaining high heat resistance.
^_1 ^_1200419315 顯像後 120°C 後 烘烤後 -—— 一 140°C 後 烘烤後 160°C 後 烘烤後 實施例1 η η η η π η Λ Λ. 比較例1 π η Λ Λ ηη 比較例2 π η Λ Λ m 實施例2 η η η η π η A Λ 實施例3 除使用設有第1圖所示5μιη之圖案與鄰接該圖之1.〇μη 線•與•間隙圖案的半色調用光罩部之光罩外，與實施例1 相同地進行圖案形成及圖案形狀之觀察。曝光所使用的曝光 裝置之理光製分檔曝光器FX_604F使製造保證解像臨界之 3.0 μ m (線•與•間隙）降低者。結果如表2所示。如表2所示 ，半色調部無法解像’結果與曝光量約一半者效果相同，顯 像後形成具有殘膜約爲一半高度之企求輪廓的圖案。而且， 可知於120°C、140°C、160°C知任何後烘烤後，形狀沒有變 化、可維持具有充分耐熱性之半色調圖案輪廓。 - 1 9 - 200419315 比較例3 除沒有進行全面曝光外，與實施例3相同地進行圖案形 成及圖案形狀之觀察。結果如表2所示。如表2所示，顯像 後於實施例3相同地形成沒有問題之半色調圖案，惟實施後 烘烤時會簡單流動，板色調部與完全未曝光相連，沒有使用 半色調方法之輪廓。 表 2 顯像後 120°C 後 烘烤後 140°C 後 烘烤後 160°C 後 烘烤後 實施例3 Γ\ Γ\ / Γ\ / \ /- \ ί V- 比較例3 r^\ / \ 實施例4 使用實施例3使用的半色調光罩者，進行光罩設計時可 製得具有波型形狀之高耐熱性圖案。換言之，不僅使用曝光 裝置之理光製分檔曝光器FX-604F使製造保證解像臨界之 3.0μπι(線•與•間隙）下降，設置2·5μπι線•與•間隙部之光 罩外’與實施例3相同地進行圖案形成及圖案形狀之觀察。 結果如表3所示。如表3所示，顯像後可得企求的波型形狀 ’全面曝光後之後烘烤，於12〇°C、140°C、160°C下不會脫離 波型形狀。 -20- 200419315 比較例4 _ k有進彳了全面曝光外，與實施例4相同地進行圖案形 成及圖案形狀之觀察。結果如表3所示。如表3所示，與實 方也例4相同地顯像後形成沒有問題之波型形狀，惟實施後烘 烤日寸簡單流動’完全無法維持波型形狀。 表3 顯像後 120〇C 後 烘烤後 140〇c 後 烘烤後 160°c 後 烘烤後 實施例4 /vvv\ 比較例4 /vvv\ r λ^ _1 ^ _1200419315 After development 120 ° C After baking After --- 140 ° C After baking 160 ° C After baking Example 1 η η η η π Λ Λ. Comparative Example 1 π η Λ Λ ηη Comparative Example 2 π η Λ Λ m Example 2 η η η η π η A Λ Example 3 In addition to using the pattern provided with 5μηη shown in Figure 1 and the 1.0μμ line adjacent to this figure, the gap The half-color of the pattern is called out of the mask portion of the mask portion, and pattern formation and pattern shape observation are performed in the same manner as in Example 1. FX_604F, a Ricoh stepped exposure device used for exposure, is used to reduce the 3.0 μm (line • and • gap) of the critical resolution. The results are shown in Table 2. As shown in Table 2, the halftone portion cannot be resolved, and the result is the same as that of an exposure amount of about half, and a contoured pattern having a residual film of about half the height is formed after development. In addition, it was found that at 120 ° C, 140 ° C, and 160 ° C, any shape was not changed after the post-baking, and the half-tone pattern profile with sufficient heat resistance was maintained. -1 9-200419315 Comparative Example 3 The pattern formation and the pattern shape were observed in the same manner as in Example 3 except that the overall exposure was not performed. The results are shown in Table 2. As shown in Table 2, a halftone pattern without problems was formed in the same manner as in Example 3 after the development, but after the bake was performed, the halftone pattern simply flowed, and the plate tone portion was connected to completely unexposed, and the outline using the halftone method was not used. Table 2 After imaging 120 ° C After baking 140 ° C After baking 160 ° C After baking Example 3 Γ \ Γ \ / Γ \ / \ /-\ ί V- Comparative Example 3 r ^ \ / \ Example 4 A person who uses the halftone mask used in Example 3 can design a highly heat-resistant pattern with a wave shape when designing the mask. In other words, not only the FX-604F, a Ricoh stepped exposure device using an exposure device, lowers the manufacturing guarantee resolution threshold of 3.0 μm (line • and • gap), and sets a 2.5 μm line • and • outside the mask of the gap 'and In Example 3, pattern formation and pattern shape observation were performed in the same manner. The results are shown in Table 3. As shown in Table 3, the desired wave shape can be obtained after development ′ After full exposure, it is baked and does not leave the wave shape at 120 ° C, 140 ° C, and 160 ° C. -20- 200419315 Comparative Example 4 _ k The pattern formation and pattern shape were observed in the same manner as in Example 4 except that full exposure was performed. The results are shown in Table 3. As shown in Table 3, the same wave shape was formed after development in the same manner as in Example 4 but the wave shape was simply not maintained after the baking process. Table 3 After development 120 ° C After baking 140 ° c After baking 160 ° c After baking After baking Example 4 / vvv \ Comparative Example 4 / vvv \ r λ
【發明之效果】 藉由本發明可形成習知組成與步驟無法形成的超高耐 熱之光阻圖案，於一般的微影術中可形成超高耐熱光阻膜、 且於作爲半色調步驟或波形形狀殘材的特殊用途中，可形成 耐熱性、乾式蝕刻耐性優異的圖案。 (五）圖式簡單說明 第1圖係爲具有半色調部之光罩例。 -2 1-[Effects of the Invention] With the present invention, an ultra-high heat-resistance photoresist pattern that cannot be formed by conventional compositions and steps can be formed, and an ultra-high-heat-resistance photoresist film can be formed in general lithography, and used as a halftone step or wave shape. In the special use of the residual material, a pattern excellent in heat resistance and dry etching resistance can be formed. (V) Brief Description of Drawings Figure 1 shows an example of a mask having a halftone portion. -twenty one-